|Publication number||US4160824 A|
|Application number||US 05/893,815|
|Publication date||Jul 10, 1979|
|Filing date||Apr 5, 1978|
|Priority date||Aug 16, 1975|
|Publication number||05893815, 893815, US 4160824 A, US 4160824A, US-A-4160824, US4160824 A, US4160824A|
|Inventors||Shinichi Inazuka, Shigekatsu Tsuchiya, Katsumi Suzuki, Toshiaki Miyanishi|
|Original Assignee||Ajinomoto Co., Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (3), Non-Patent Citations (4), Referenced by (20), Classifications (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a continuation, of application Ser. No. 714,126, filed, Aug. 13, 1976, now abandoned.
1. Field of the Invention
This invention is concerned with insect attractive compositions.
2. Description of the Prior Art
Thus far, insect attractants have been used with or without other drugs for the control of insects by means of surveying and monitoring of pest populations, mating disturbance, killing by luring with insecticide, attracting natural enemies of insects, etc. These are roughly classified into the food-type attractants and the other attractants (such as sex attractant). The former are, in particular, known to be widely effective against insect imagines irrespective of their sex, stage of emergence, or age, though its activity is extremely low as compared with that of a sex attractant. For example, acid-hydrolyzed (protein hydrolysis percent<70%) soy bean cakes (soy bean liquid) are used to control fruit flies but they are not effective enough because of their low activity to the insect.
After many efforts to overcome the shortcomings of acid-hydrolyzed soy bean cakes (soy bean liquid) which have been used so far, the present inventors have succeeded by finding that highly hydrolyzed (protein hydrolysis percent<70%) defatted cereals which have been neutralized, preferably, after being concentrated 2 to 10 times in strongly acidic media, are more greatly insect attractive than are the hydrolyzed soy bean cakes (soy bean liquid) (protein hydrolysis percent<70%) conventionally used as attractants. Moreover, it has been found that they are effective even for those insects which are hardly attracted by the soy bean cakes (soy bean liquid). The deffated cereals of this invention include those of soy bean, corn, cotton-seed, rape-seed, sesame, etc.
The acid-hydrolysates used in this invention can be prepared by conventional methods. For instance, defatted cereals can be hydrolyzed with mineral acids such as sulfuric acid or hydrochloric acid and heat applied where necessary.
Determination of the protein hydrolysis percent is made by the well known Formol titration method and Kjedahl method which the Formol type nitrogen and the total nitrogen, respectively, to yield ##EQU1##
In order to prepare the insect attractive compositions of this invention from the hydrolysates thus obtained, impurities such as humus and inorganic substances are removed from the hydrolysates. More simply, the hydrolysates are, preferably, concentrated 2 to 10 times in acidic media (pH 4 to 7), more suitably 3 to 5 times, after being treated with an alkali such as NaOH, KOH, soda lime, ammonia, etc., and then neutralized to give a pH 5 to 9.
An example is given below for preparation of the insect attractive compositions.
One kilogram of defatted soy bean and 1.48 kilograms of hydrochloric acid (22%) are mixed and heated for 20 hrs at 115° C. with stirring. Humus is separated from the hydrolysate by filtration. The filtrate is concentrated 3 times by heating and neutralized with NaOH solution (20%) to make the pH of the solution 6.5. This way, about 3 kilograms of the product are obtained. The protein hydrolysis percent was 75.5% in this case.
The mixture obtained above can be used as is for an insect attractive composition of this invention. It can also be used as an insect attractive composition in the form of a solution, an emulsion, a wettable powder, a dust, granule, or an aerosol if it is dissolved or dispersed in a suitable liquid carrier (e.g., a solvent), or mixed with or adsorbed on a suitable solid carrier (e.g., a dust diluent and carrier), with the aid of an emulsifier, dispersing agent, suspending agent, spreading agent, penetrant, wetting agent, or stabilizing agent, where necessary.
Suitable solvents for the insect attractive compositions of this invention include water, alcohols (e.g., methyl alcohol, ethyl alcohol, ethylene glycol), ketones (e.g., acetone, methyl ethyl ketone), ethers (e.g., dioxane, tetra-hydrofuran, methyl cellosolve), aliphatic hydrocarbons (e.g., gasoline, kerosene, lamp oil), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent naphtha), organic bases (e.g., pyridine), halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride), acid amides (e.g., dimethyl formamide), esters (e.g., ethyl acetate, butyl acetate, fatty acid glycerides), nitriles (e.g., acetonitrile), and sulfur compounds (e.g., dimethyl sulfoxide). They are usually used alone or as mixtures of two or more components.
As dust diluents or carriers are used botanical powders (e.g., soy bean powder, tobacco powder, wheat flower, wood powder, etc.), mineral powders (e.g., clays like kaolinite, bentonite, and acid earth, talcs like phylite, silicas like diatom earth and mica), alumina, sulfur powder, and active charcoal. These powders can also be employed separately or as mixtures of two or more components.
Useful emulsifiers, spreading agents, and penetrants are soaps, sulfuric acid esters of higher alcohols, alkyl sulfonates, alkylaryl sulfonates, quarternary ammonium salts, fatty acid esters of oxyalkylamines, polyalkylene oxides, and sorbitols.
Where necessary, casein, gelatine, starch, alginic acid, agar, CMC, polyvinylalcohol, wood turpentine, rice-bran oil, sucrose, glucose, molasses, aminoacids, etc. can be added.
The insect attractive compositions of this invention can also be used with insecticides (chlorinated hydrocarbons, organic phosphorous compounds, carbamates, natural insecticides) synergic agents, other kinds of attractants, perfumes, germicides, etc.
The insect attractive compositions described above in detail are strongly insect-attractive and can be used with or without insecticides to survey, monitor, and control insect damage to human beings, animals, and plants. The acid-hydrolysates of proteins used in this invention are harmless to men and beasts.
They are effective against the insects of the classes Culicidae, Muscidae, Cecidomylidae, Trypetidae, Drosophilidae, Calliphoridae, Sarcophagidae, Agromyzidae, Tabanidae, etc.; of the classes Diptera, Blattidae, Blattellidae, etc.; of the classes Orthoptera, Myrmeleonidae of Heoroptera, Noctnidae, (Adristyrannus amurensis Staudinger, Oraesia excavata Butler, Oraesia emarginata Fabricius, Heliothis assulta guenee, Prodenia litura Fabricius, etc;) of the classes Lapidoptera, Yponomeutidae (e.g., Plutilla maculipennis Curtis), Carposinidae (e.g., Carposina niponensia Walsingham), Lymantrudae, etc.
A spherical insect attracting trap (McPhail trap) was fixed at the upper central part of a large-sized steel wire cage (200 cm×200 cm×200 cm).
Twenty five ml of a 1% sample solution (containing an insecticide) were placed in the trap. After allowing the system to stand for 24 hrs, the number of killed insects was counted.
The sample consisted of HCl-hydrolyzed defatted soy bean and corn cakes which were neutralized to give a pH of 5 with NaOH after being concentrated 3 times. The protein hydrolysis percentages had the values of 30, 40, 50, 60, 70, 80, and 90%. The total nitrogen was adjusted to 3.0 g/dl. The insects used were those of Hylemyria platura Meigen, Chlorops oryzae Matsumura, Plutella xylosetella Linnaeus, and Culex pipiens pallens. They were 1000 female imagines at the 4th day after emergence. The sample solution contained an insecticide (Sumithion). Table 1 gives the number of killed insects after a definite time. Larger number correspond to higher attractiveness. The table indicates clearly that all the samples made from highly hydrolyzed proteins (protein hydrolysis percent≧70%) of defatted soy bean and corn cakes are strongly attractive to flies employed in this Example.
Table 1__________________________________________________________________________ Acid decomposition- Acid decomposition- concentration of defatted concentration of defatted soy bean corn Protein Hylemyria Chlorops Plutella Culex Hylemyria Chlorops Plutella Culex hydrolysis Platula Oryzae Xylostella pipiens Platula Oryzae Xylostella pipiens percent Meigen Matsumura Linnaeus Pallens Meigen Matsumura Linnaeus Pallens__________________________________________________________________________ 30% 0 1 0 0 1 1 0 1Control 40 1 2 1 2 1 1 2 1 50 3 3 1 2 3 4 3 3 60 4 2 3 3 4 2 6 3Present 70 29 19 12 15 31 20 18 11Invention 80 25 22 15 12 26 17 27 45 90 23 18 12 17 25 14 30 29__________________________________________________________________________
One kilogram of defatted soy bean and 1.48 kilograms of hydrochloric acid (22%) were mixed and heated for 20 hrs at 115° C. with stirring. Humus was then separated from the reaction mixture by filtration. The filtrate was concentrated 3 times under the conditions indicated in Table 2. The pH of the solution was brought to 6.7 by adding an alkali. By using the sample thus prepared attractive tests were performed on Musca domestica Linner flies. The results obtained are given in Table 2. The insects used were 1000 female imagines of Musca domestica Linner at the 4th day after emergency. The method of testing was the same as that adopted in Example 1. Data were taken in duplicate 48 hrs after the start of the test and averaged.
Table 2______________________________________ Number of killedSample Conditions of concentration insects Evaluation______________________________________1 Strongly acidic (pH < 3) 71 ++2 Weakly acidic or neutral 5 ± (pH 5-7)3 Alkaline (pH = 8) 3 ±4 Non-concentrated 17 +______________________________________
As is clear from Table 2, concentration of the hydrolysate at a strongly acidic pH gives a remarkable attractive effect on the insect. The same trend was found for other insects.
A mixture consisting of one part of HCl-hydrolysate of defatted soy been cake (protein hydrolysis percent=75%, neutralized with NaOH, total nitrogen=3 g/dl), one part of insecticide (DDVP:emulsifier32 1:1), and 98 parts of water was sprinkled over a paddy filed. As a result, it was found that not only is the mixture very effective against the target insect but also it reduces the frequency of required sprinkling and raises the size of the rice crop as compared with a mixture of the same composition using a different HCl-hydrolysate of soy bean cake (protein hydrolisis percent=40%).
A mixture of ten parts of HCl-hydrolysate of defatted corn cake (protein hydrolysis percent=85%, neutralized with NaOH, total nitrogen=4.5 g/dl), 10 parts of insecticide (MEP:emulsifier=1:1), 10 parts of crude sugar, 10 parts of alginic acid, and 60 parts of water was sprinkled over a peach orchard. This mixture was found to kill the target insects (e.g. peach fruit moth) effectively and reduce damage from the insects drastically.
A McPhail trap shown in FIG. 2 was hung down from the ceiling of a trap type olfactometer depicted in FIG. 1. The olfactometer was a plastic box (100 cm×100 cm×100 cm) and had a steel wire cover on the top. A motor was fixed at the center of the ceiling of the olfactometer to rotate the hanger to which the trap is attached as shown in FIG. 3. At the center of the bottom of the olfactometer a dish and a pot were placed. They contained some cubes of sugar and water, respectively, as baits for the target insects. A tangle food was applied on the legs of the olfactometer.
The target insects were 100 each of male and female melon flies at the 3rd day after emergency. Each of the traps contained 20 ml each of the samples A to C, below, and was rotated at a constant speed of 1/15 r.p.m. The number of killed insects in each olfactometer was counted over 17 hrs from 5 p.m. to 10 a.m.
The results obtained are given in FIGS. 4 and 5, which indicate that the hydrolysates of soy bean protein and cotton seed protein are strongly insect-attractive at pH higher than 5 if they have been hydrolyzed and concentrated to give the same protein hydrolysis percent and the same concentration.
______________________________________Sample Content______________________________________A Insecticide alone (Malathion emulsion) 1000 times dilutedB Soy bean protein hydrolysate (protein hydrolysis percent = 70%, 3 times concentrated, pH = 1.0-9.0, total nitrogen = 3.0 g/dl) 10 parts Insecticide (Malathion emulsion) 1 part 1000 times dilutedC Cotton seed protein hydrolysate (protein hydrolysis percent = 75%, 3 times concentrated, pH = 1.0-9.0, total nitrogen = 3.0 g/dl) 10 parts Insecticide (Malathion emulsion) 1 part 100 times diluted______________________________________
A field test was carried out at Ishiki, Itoman City, Okinawa Prefecture (Southern part of Okinawa Island), Japan. Traps of the type shown in FIG. 2 were hung from branches of trees and 100 ml of the sample solutions were sprinkled with a hand spray on the surface of the leaves of the trees right above the traps. Next day, the numbers of killed Melon flies and Oriental fruit flies were counted.
The samples used were as follows.
______________________________________D Insecticide (Malathion emulsion), 1000 times diluted. Commercially available acid-hydrolysate of plant proteins*E Insecticide (Malathion emulsion) 10 parts 100 times diluted 1 part *"PIB7" ® (A product of Staley Co., Ltd., U.S.A., Protein hydrolysis %: 47%)
Commercially available acid-hydrolyzed soy bean proteins*F Insecticide 10 parts 100 times diluted 1 part *"Nasiman" ® (A product of Israel)
(Protein hydrolysis percent: 40 and 70%, 3 timesG concentrated, pH 6.5, total nitrogen: 3.0 g/dl) Insecticide (Malathion emulsion) 1 part 100 times diluted Acid-hydrolysate of corn proteins 10 parts (Protein hydrolysis percent: 40 and 70%, 3 timesH concentrated, pH 6.5, total nitrogen 3.0 g/dl) Insecticide (Malathion emulsion) 1 part 100 times diluted______________________________________
The results of the above field test are summarized in Table 3, in which the hydrolysates in this device show a high activity.
Table 3__________________________________________________________________________Proteinhydroly- Number of attracted fliessis Melon fly Oriental fruit flySample percent PH ♀ ♀ ♀ + ♂ ♀ ♀ ♀ +♂__________________________________________________________________________D -- -- 0 0 0 0 0 0E 47% 4.8 1.0 ± 1.0 2.0 ± 1.0 3.0 ± 2.0 0.5 ± 0.5 1.0 ± 1.0 1.5 ± 1.5F 65.5 4.39 1.0 ± 1.0 1.0 ± 1.0 2.0 ± 2.0 0.5 ± 0.5 2.0 ± 1.0 2.5 ± 0.5G 40 6.5 2.0 ± 1.0 2.0 ± 0 4.0 ± 1.0 2.0 ± 1.0 1.0 ± 1.0 3.0 ± 2.0" 70 6.5 7.5 ± 0.5 4.5 ± 1.5 12.0 ± 1.0 5.5 ± 1.5 6.0 ± 1.0 11.5 ± 2.5H 40 6.5 2.0 ± 1.0 2.0 ± 1.0 4.0 ± 2.0 2.0 ± 2.0 2.0 ± 1.0 4.0 ± 1.0" 70 6.5 10.5 ± 2.5 5.0 ± 2.0 15.5 ± 4.5 8.5 ± 1.5 4.0 ± 1.0 12.5 ± 2.5__________________________________________________________________________
An indoor test was performed using the same apparatus as in Example 5. The trap was rotated at a constant rate of 1/15 r.p.m. After a definite period of time, the number of killed flies in the trap was counted.
Testing period: 17 hrs from 5 p.m. to 10 a.m.
______________________________________Target flies(1) Melon flies 100 each of male and female insects at the 3rd day after emergency(2) Oriental fruitflies 100 each of male and female insects at the 3rd day after emergencyBaits for the flies Cubes of sugar and waterSample solutions 20 ml each of the samples I to L were placed in McPhail trapsI Insecticide (Malathion emulsion) alone, 1000 times diluted Commercially available acid-hydrolysate of soy bean proteins 10 partsJ "PIB-7" ® (A product of A.E. Staley Co., Ltd., U.S.A., Protein hydrolysis percent: 47%, pH 4.8) Insecticide (Malathion emulsion) 1 part 100 times diluted Acid-hydrolysate of soy bean proteins 10 parts (Protein hydrolysis percent: 20-90%, 3 timesK concentrated pH 6.5. total nitrogen 3.0 g/dl) Insecticide (Malathion emulsion) 1 part 100 times diluted Acid-hydrolysate of corn proteins 10 parts (Protein hydrolysis percent: 20- 90%, 3 timesL concentrated pH 6.5, total nitrogen 3.0 g/dl) Insecticide (Malathion emulsion) 1 part 100 times diluted______________________________________
The results of the test are given in Table 4. ##EQU2## The higher the index is, the higher is the activity. As is indicated in Table 4, the activity of the acid-hydrolysates of soy bean proteins and corn proteins increases remarkably when their protein hydrolysis percent exceeds 70%.
Table 4__________________________________________________________________________ Protein hydroly- Insect-attractiveness index sis Melon fly Oriental fruit flySample percent PH ♀ ♂ ♀ + ♂ ♀ ♂ ♀ + ♂__________________________________________________________________________I -- -- 0 0.2 0.1 0 0.5 0.3J 47 4.8 1.0 1.0 1.0 1.0 1.0 1.0 20 6.5 0.8 0.5 0.7 1.0 0.8 0.9ControlK 40 6.5 1.2 1.5 1.3 1.4 1.7 1.6 60 6.5 2.0 1.8 1.9 1.8 1.5 1.6 20 6.5 0.5 0.9 0.7 0.8 1.5 1.3L 40 6.5 1.5 2.4 1.9 1.6 0.9 1.1 60 6.5 2.2 2.0 2.1 2.0 1.0 1.3 70 6.5 4.8 5.0 4.9 3.9 2.0 2.6PresentK 90 6.5 4.7 5.3 5.0 4.5 3.0 3.5Invention 70 6.5 5.3 6.2 5.7 4.0 1.4 2.3L 90 6.5 5.0 7.0 5.9 4.3 1.2 2.2__________________________________________________________________________
The results of a comparative test using commerciably available "PIB-7" (U.S.A.), "Nasiman" (Israel), and a sample in this invention are shown in Table 5.
Table 5__________________________________________________________________________ Product of "PIB-7"® "Nasiman"® this invention*pH 4.80 4.39 6.50NaCl 12.63 g/dl 14.34 g/dl 15.0 g/dlTotal N 3.79 2.96 4.87NH3 form N 0.49 0.68 0.60Formol form N 1.79 1.94 3.61Protein hydrolysis percent 47.2% unknown 74.0 %__________________________________________________________________________ Lys HCl 679 mg/dl 547 mg/dl 2,271 mg/dl His HCl 282 309 1,025 Arg HCl 806 694 1,986 Asp 998 1,034 3,481 Threo 522 453 1,139 Serine 976 853 1,590Amino Glu 1,127 4,216 5,865Acid Pro 1,641 1,953 1,696 Gly 382 624 1,143 Ala 1,584 612 1,526 Cys H (+) (+) (+) Val 562 499 1,212 Met 236 31 273 I Leu 238 385 1,259 Leu 910 1,023 2,865 Tyr 162 125 582 Phe 669 584 1,513 Total 11,174 13,942 29,426 PCA 2,011 224Organic Lact 3,273 382 Acet 198 134Acid Lev 987 4,675 Form 362 631 Cit 185 2,049 Succ 50 78__________________________________________________________________________
FIGS. 1, 2, and 3 show respectively a trap type olfactometer, a McPhail trap, and rotation of the trap. Here, (a) is a motor, (b) a steel wire cover, (c) a plastic box, (d) a water pot, (e) a sugar dish, (f) legs, (g) sample, (h) a McPhail trap, (i) a hanger, and (j) a motor.
FIGS. 4 and 5 give the results obtained in Example 5 using the samples B and C.
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|U.S. Classification||424/84, 426/1, 514/122|